Producing phosphorus containing amino resins and flameproofing organic textiles



United States Wilson A. Reeves and John D. Guthrie, New Orleans,

La., assignors to the United States of America as represented by theSecretary of Agriculture Application September 3, 1953, Serial No.378,437 1 19 Claims. (Cl. 260-2) (Granted under Title 35, U. S. Code(1952), sec. 266) No Drawing.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, for all governmental purposes, throughout the world,with the power to grant sublicenses for such purposes, is hereby grantedto the Government of the United States of America.

This invention relates to new phosphorus and nitrogen containingpolymers, processes for their production and processes of employingthese polymers in the flameproofing of, certain organic fibrousmaterials.

This application is a continuation in part of our copendingapplications, Serial Nos. 283,743 filed April 22, 1952, now Patent No.2,668,096, and 283,744 filed April 22, 1952, now abandoned.

Our co-pending application, Serial No. 378,435, filed of even date,relates to certain processes employing such polymers.

In general this invention relates to polymers capable of being producedby the reaction of a phosphorus compound of the group tetrakis(hydroxymethyl) phosphonium chloride, tris(hydroxymethyl) phosphine oxide andmixtures thereof, with a monomeric nitrogen compound which contains atleast two members of the group, hydrogen atoms and methylol (CH2OH)radicals, attached to trivalent nitrogen atoms; and to processes ofreducing the combustibility of hydrophilic fibrous organic materials.

We have discovered that tetrakis(hydroxymethyl) phosphonium chloride andtris(hydroxymethyl) phosphine oxide,

('JH2OH HOCHz-P-CHzOH o1- and onion HOGHr-P= CHzOH react with monomericaliphatic compounds containingat leastytwo' members of the grouphydrogen atoms and methylol radicals, CHzOI-I, attached to trivalentnitrogen atoms, to produce polymers. The polymers which are produced arecross-linked phosphorusv and nitrogencontaining polymers in which therecurring structural units each contain a phosphorus atom that is acomponent of a radical of the group tetramethylene phosphonium chloride,(CH2)4PCl, and trimethylene phosphine oxide, (CH2)3P=?O, and is linkedto at least, two

trivalent nitrogen atoms by connecting structures of the .atent Osynthetic resins.

are members of a trimethylene phosphine oxide group and which are linkedto trivalent nitrogen atoms by connecting structures of the groupconsisting of -CH2OCH2 and CH2-.

Such polymers can be produced in the form of solid Such resins can bedeposited on the surfaces and/or in the interstices of hydrophilicfibrous organic materials, i. e., organic materials which absorb oradsorb water on most of their surface area. When such resins are sodeposited, they reduce the combustibility of hydrophilic fibrous organicmaterials and resist removal by laundering and the like chemicaltreatments. Such resins can be deposited on the surfaces ofnonhydrophilic materials to form flame resistant coatings.

We have also discovered that tetrakis(hydroxymethyl) phosphoniumchloride and tris(hydroxymethyl) phosphine oxide react with polymericaliphatic compounds containing at least two members of the groupconsisting of hydrogen atoms and methylol (-CI-IzOH) radicals attachedto trivalent nitrogen atoms, other. than the aminoalkylated cellulosesdisclosed in our application Serial No. 283,743. Such reactions providevaluable new processes and products.

In the case of polypeptides, such mers such as poly(hexamethyleneadipamide), the

, reaction provides an improved process of coagulating and precipitatingthe polypeptide. In addition, the products of this reaction are valuablenew polypeptides containing recurring structural units composed ofphosphorus atoms which are members of a pentavalent phosphorus radicalof the group consisting of' a trimethylene phosphine oxide and atetramethylene phosphonium chloride radical, and which phosphorus atomsare linked to trivalent nitrogen atoms by connecting structures of thegroup consisting of -CH2OCH2 and CH2.

In the case of open chain polyamines such as tetramethylenepentamine thereaction produces valuable new polyamines exhibiting, to a rather widelyvariable, controlled degree, the properties of a thermosettingnoncombustible polymer. Such polymers contain the phosphorus andnitrogen groups of the type described above. V H I In the case ofmonomeric alicyclic compounds containing at least two members of thegroup consisting of hydrogen atoms and methylol (-CH2OH) radicalsattached to trivalent nitrogen atoms, such as cyclohexylamine thereaction produces valuable new flame-resistant polymers containingalicyclic rings and the above described type of phosphorus and nitrogengroups.

' In the case of monomeric aromatic compounds containing at least twomembers of the group consisting of hydrogen atoms and methylol (--CH2OH)radicals attached to trivalent nitrogen atoms, such as aniline thereaction produces valuable'new flame-resistant polymers containingaromaticring s and the above described type of phosphorus and nitrogengroups.

. In the case of cyclic imines such as ethylenimine and its homologs,the reaction produces unique and valuable new polymers containing theabove described type of phosphorusv and nitrogen groups, plus, in thecase of ethylenimine and its homologs, groups in which the same nectingstructures of the general group, i v

--C(R)2C(R)I2OCH2 and CHzin which R represents radicals of the groupconsisting of hydrogen and alkyl radicals. Such polymers exhibit theunique property of sorbing relatively large amounts of water andswelling, during the sorbtion. I In the case of an organic compoundcontaining asingle member of the group consisting of hydrogen atoms-andas proteins, and polymethylol groups attached a trivalent nitrogen atom,such as dimethylamine, 'N,N-diethyl methylolamine, N-allylcyclohexylamine, or phthalamide, the reaction produces valuable newcompounds containing a recurring structural unit composed of phosphorusatoms which are members of a pentavalent phosphorus radical of the groupconsisting of a trimethylene phosphine oxide and a tetramethylenephosphonium chloride radical, and which phosphorus atoms are linked totrivalent nitrogen atoms by connecting structures of the groupconsisting of, CH2OCH2- and -CHz-. New compounds of this type in whichthe phosphorus atoms are attached to a plurality of methylol radicalsreact with the various classes of nitrogen compounds in the same waythat the phosphorus compounds from which they were prepared react; andthose in which the phosphorus atom is attached to a single methylolradical react in the same way, except that they are monofunctional.

We have also discovered that incompletely polymerized, i. e., water ororganic solvent soluble polymers of such phosphorus compounds withmonomeric organic compounds containing at least two members of the groupconsisting of hydrogen atoms and methylol (CH2OH) radicals attached totrivalent nitrogen atoms can be quickly and advantageously insolubilizedby reacting the polymers with ammonia. The ammonia can be employed inthe form of an aqueous solution. This insolubilization can beaccomplished at low temperature and can be used to combine additionalnitrogen into the polymer.

The compounds, tetrakis (hydroxymethyl) phosphonium chloride andtris(hydroxymethyl) phosphine oxide, are hereinafter referred to bytheir initials THPC and THPO. The term phosphorus compounds is employedto refer to THPC or THPO, or mixtures of THPC and THPO. The termnitrogen compound is employed to refer to monomeric aliphatic compoundscontaining at least two members of the group consisting of hydrogenatoms and methylol (CH2OH) radicals attached to trivalent nitrogenatoms.

Illustrative examples of suitable nitrogen compounds include: (1) aminocompounds such as urea and urea derivatives like methylol ureas,alkylated methylol ureas, oxalyl urea and hydantoin, melamine andmelamine derivatives like methylol melamines, alkylated methylolmelamines, alkyl substituted melamines where the alkyl group or groupsare either saturated or unsaturated and guanidine, hydrazine andhydroxylamine, (2) aliphatic amines such as ethylamine, ethylenediamine,allylamine and cetylamine, (3) amides such as formamide, *butyramide,octadecylamide an'd acrylamide and (4) amino acids such as glycine,lysine and arginine.

The polymers provided by this invention can be formed by reacting thephosphorus compounds with: (1) mixtures of the nitrogen compounds; (2)one or more of the nitrogen compounds and formaldehyde. In the lattercase, the phosphorus compounds can be incompletely reacted with thenitrogen compounds prior to reaction with formaldehyde, or the nitrogencompounds can be incompletely reacted with formaldehyde prior toreaction with the phosphorus compounds, or the phosphorus compounds, thenitrogen compounds and formaldehyde can be concurrently reacted.

Hydrophilic fibrous organic materials are rendered less combustibleby'impregnating the materials with aqueous solutions, or homogeneousdispersions, of the respective monomers, or partially reacted monomers,and curing the impregnated materials.

Melamine, urea, and water-soluble methylolmelamines and methylolureasare preferred members of the nitrogen compounds; and THPC and mixturesof TH'PC and TI-IPO are preferred members of the phosphorus compounds.

The polymers provided by this invention can be produced in the form ofliquids or solids and can be molded by the conventional techniques ofmolding thermosetting resins. These polymers are valuable materials foruse in the production of molded synthetic plastic articles, such asbuttons, food containers, electrical insulators and the like; syntheticcoatings such as protective coatings, and paints, varnishes and the likehaving a reduced flammability due to the presence of some of thepolymers; adhesives, such as the amino resin type adhesives having areduced flammability due to the presence of some of the polymers; papertreating resins; textile resins; and the like.

The terms parts and percent as used herein refer to parts or percent byweight.

Condensation polymers of THPC and THPO with the nitrogen compounds arepreferably prepared by agitating a mixture of the phosphorus andnitrogen compounds in water while heating until polymerization occurs.The preferred relative amounts of phosphorus and nitrogen compounds usedto polymerize can be calculated by con ventional methods used forcondensation polymerization by assuming that: (1) THPC istetrafunctional and THPO is trifunctional, (2) one methylol group of thephos phorus compound condenses with one hydrogen or methylol groupattached to a trivalent nitrogen atom of the nitrogen compound, and (3)THPC is converted to THPO in the presence of neutral carbonates likecalcium carbonate, alkali carbonates like sodium carbonate, alkali metalhydroxides, tertiary amines like triethanolamine, and bases in general.

For example the mole ratio range for polymerizing THPC with melamine isone mole of THPC per 0.2 to 2 moles of the amino compound with thepreferred range of 0.3 to 1.3 mole of the amino compound per mole ofTHPC. When THPO is polymerized with melamine the mole ratio range is oneof THPO per 0.15 to 2 moles of the amino compound with the preferredrange of 0.3 to 1.0 mole of the amino compound per mole of THPO. TheTHPO can be made in situ as described above. To polymerize THPO withurea the mole ration range is one mole of THPO per 0.25 to 3.0 moles ofurea with the preferred range of 0.6 to 2.0 moles of urea per mole ofTHPO. To polymerize THPO with acrylamide the mole ratio range is onemole of THPO per 0.5 to 4.0 moles of acrylamide with the preferred moleration range of 1.0 to 2.5 moles of acrylamide per mole of THPO.

THPC and/ or THPO will copolymerize with materials which are inthemselves capable of polymerizing (e. g., methylolmelamine) over anextremely wide range. For example trace quantities of THPC and/or TI-IPOadded to essentially a aqueous solution of methylolmelamine willco-polymerize with the methylolmelamine to produce a new phosphorus andnitrogen containing resin. These new phosphorus and nitrogen polymersare formed until there exists in the aqueous solution about 4 moles ofthe THPO or THPC per one mole of the methylolmelamine.

Polymerization reactions conducted in accordance with the process ofthis invention can be carried to the extent of producing solid, liquid,or gel-like polymers. The liquid polymers can be isolated from thereaction medium by dissolving inthe reaction medium a selective solventfor water. Methyl, ethyl, and isopropyl alcohols are preferred selectivesolvents. The polymerization of isolated partial polymers can becompleted by conventional procedures of thermally completing thepolymerization of partially polymerized thermosetting monomers.

The polymerization reaction can be conducted in the presence of minoramounts of water soluble acidic or basic reacting compounds. Preferredacid reacting compounds are acetic or hydrochloric acid and the acidcatalysts conventionally used in the production of amino resins. Thealkali metal carbonates, bicarbonates and triethanolamine are preferredbasic reacting compounds.

The combustibility of organic fibrous materials can be reduced inaccordance with this invention by impregnating the fibrous materialswith an aqueous solution, or

uniform suspension or dispersion, of the monomeric compounds, or thepartially polymerized monomers formed by reacting the monomericcompounds until partial polymerization occurs; and curing theimpregnated materials at the elevated temperatures conventionally usedfor curing fibrous organic materials.

The process of this invention can be used to reduce the combustibilityof substantially any hydrophilic fibrous material such as cotton, rayonsuch as viscose rayon, ramie, jute, wool, paper, cardboard, and the likematerials which can be impregnated with a liquid, dried, and cured.

Where the organic fibrous material consists of a textile fiber orfabric, the hydrochloric acid resulting from THPC in the'partialpolymerization reaction or in the complete polymerization is preferablyneutralized with a water soluble basic or base forming compound. Thealkali metal bicarbonates and carbonates, guanidine carbonate,triethanolamine, diethanolamine, and urea are preferred basic reactingcompounds. Diethanolamine reacts with the phosphorus compounds to becomea part of the polymeric material. The basic or base forming compound orcompounds can be added to the reaction medium before, during or afterthepartial polymerization of the monomers.

Where a textile is being impregnated, it is of advantage to remove theexcess impregnating liquid by passing the textile through squeeze rollsadjusted to. apply a comparatively extremely high pressure prior todrying and curing the impregnated textile. It is also of advantage todry the textile at a temperature of about 70 C. to 110 C. before it iscured at a temperature of from about 110 C. to 180 C. p

The degree of flameproofing imparted to a textile by these phosphorusand nitrogen resins can be varied from a low degree to a very highdegree by varying the amount of polymer put in the fabric.

Some advantages of flameproofing textiles in accordance with thisinvention are: textiles treated by this process are flame resistant,glow resistant, shrink resistant, wrinkle resistant, rot resistant, andmildew resistant; the effects of the treatment are permanent, andresistant to laundering, dry cleaning, boiling alkali solutions and acidtreatments.

The following examples are illustrations of the invention:

Example 1 A mixture of tetrakis(hydroxymethyl) phosphonium chloride andabout /3 part of melamine was mixed with approximately 1% parts ofwater. The mixture was agitated for about 20 minutes at from 80 to 90 C.and a clear solution resulted. 'The hydrochloric acid formed during thereaction was neutralized by adding calcium carbonate until the rate ofevolution of carbon dioxide decreased.

The neutralized clear solution polymerized almost immediately. Aftercuring at about 110 C. for about 1 hour, the resulting thermosettingresin was noncombustible and contained 12.5% phosphorus, 2.21% chlorine,and 24.1% nitrogen.

Example 2 A mixture of tetrakis(hydroxymethyl) phosphonium chloride and0.3 part of melamine was agitated with about 3.5 parts of water at 65 C.until a clear solution was formed. Sodium carbonate was slowly stirredinto the warm solution until the rate of evolution of carbon dioxidedecreased. The resultant solution remained clear when cooled to roomtemperature. Heating a relatively thin layer of solution for aboutminutes at about 130 C. produced a clear noncombustible thermosettingresin.

After standing about 24 hours at room temperature a portion of the clearsolution in a container in which it presented a relatively small surfacearea in comparison with its volume became a clear sirup which was nolonger soluble in water.

Example 3 p A mixture of tetrakis (hydroxymethyl) phosphonium chlorideand 0.4 part of melamine was mixed with ap proximately 1.5 parts ofwater containing a minor amount of acetic acid and diammonium phosphate.The mixture was agitated for about 20 minutes at about to C. resultingin a clear solution containing a small amount of suspended solid. Thesolid was removed by centrifugation. j

Heating a thin layer of this clear solution for 10 minutes at C.produced a substantially clear resin insoluble in: aqueous 15%formaldehyde; aqueous 20% sodium hydroxide; and glacial acetic acid. Theresin was noncombustible. a

On standing about 24 hours atroom temperature the clear solution gelled.The gel was cured at 110 C. for 2 hours and produced a noncombustiblethermosetting resin containing 12.1% phosphorus and 21% nitrogen and 11%chloride. 7

Example 4 A mixture of tetrakis (hydroxymethyl) phosphonium chloride and1 part of guanidiue was agitated with about 2 parts of water at about 25C. until a clear solution was produced.

After about 72 hours at room temperature the clear solution became aclear viscous sirup which was no longer soluble in water.

Example 5 A mixture of tetrakis (hydroxymethyl) phosphonium chloride andabout 1 part of urea was agitated with about 2 parts of water at about100 C. for about 15 minutes, then cured at C. for 25 minutes. Theresultant product was a hard and clear water soluble material.

Example 6 Tetrakis (hydroxymethyl) phosphonium chloride was mixed withapproximately 1 part of a mixture of melamine and'about 3 molar portionsof formaldehyde which had been reacted sulficiently, by heating, to forma water soluble mixture and the resulting mixture was mixed withapproximately 2 parts of water. The resulting aqueous mixture wasagitated at about 60 C. for about 15 minutes at which time it became adough-like mass. When heated for about 30 minutes at about 80 to 90 C.and allowed to stand for about 24 hours at room temperature thedough-like mixture was converted to a water insoluble polymer.

Example 7 A cotton print cloth was mercerized in about 20% lye, washed,run through squeeze rolls then padded with a solution prepared by mixingtetrakis (hydroxymethyl) phosphonium chloride with about 0.8 part of amixture of melamine and formaldehyde, which had been partially reacteduntil the mixture was water soluble, and with about 2 parts of water.The impregnated cloth was dried at 55 to 65 C. and cured for 4 minutesat C.

After the fabric was washed in hot tap water for 10 minutes and dried,it would do the angle flame test and was not stiff.

Example 8 The resultant fabric had a similar flame resistance and wastendered only slightly.

Example 9 A cotton print cloth was padded with a neutral solution madeby heating a mixture of six parts of tetrakis (hydroxymethyl)phosphonium chloride with two parts;

' 7 of melamine and sufficient sodium carbonate to make to pH 7. Thepadded fabric was first dried at 70 C. then cured four minutes at 150 C.

After washing the fabric would do the 170 flame tests.

Example An eighty square cotton print cloth was mercerized inapproximately sodium hydroxide, washed well, then run through squeezerolls to remove the excess water, and then padded with a solutionconsisting of one part tetrakis (hydroxymethyl) phosphonium chloride,about 0.8 part of a mixture of melamine and formaldehyde (previouslyreacted to produce a water soluble mixture), about 0.4 part of urea, andabout 2 parts by weight of water. The padded fabric was dried at to C.and cured 4 minutes at 150 C.

After two treatments with 0.1% Igepon T solution at 60 C. and an acidsour with 0.02% sodium silicofluoride, the fabric was flameproof.

The treated fabric before and after l epon T treatment exhibited wrinkleresistance.

The treated fabric was subjected to the vertical flame test before andafter the Igepon T treatment. Before washing the length of rip afterburning was 3 /8, after washing the length of rip after burning was 3 7There was no afterglow in either case. Considering the weight of thefabric, the above values are well within the maximum values recommendedby the Quartermaster Corps for fiameproofing cotton cloth.

Example 11 A mixture of one part tris(hydroxymethyl) phosphine oxide andone part of melamine with five parts of water was heated to about C.until a clear solution formed.

When the clear solution was spread out in a thin layer and heated at C.,a clear hard polymer formed which was insoluble in water, alcohol,alkali or acids.

Example 12 A mixture of one part of tris(hydroxymethyl) phosphine oxideand one part of urea was dissolved in 4 parts of water and then boiledfor 60 minutes. This produced a clear jell. When the jell was heated at140 C. for 20 minutes a hard insoluble polymer was produced.

Example 13 One part of tris(hydroxymethyl) phosphine oxide and 1.3 partsof tetrakis(hydroxymethyl) phosphonium chloride were mixed with one partof melamine in 5 parts of H20 and heated to boil. A clear solutionformed and then with 5-10 minutes of boiling, jellation occurred. Thejell was clear; when it was heated to C. it became hard and insoluble.

Example 14 Cotton fabric (8 oz. twill) was padded with a solution madefrom 3 parts of tris(hydroxymethyl) phosphine oxide, 13 parts oftetrakis(hydroxymethyl) phosphonium chloride, 10.5 parts of urea, 10.5parts of a water soluble trimethylol melamine and 63 parts of water. Thesolution had a pH of 6.8. The impregnated fabric was dried for 4 minutesat 85 C. The dry fabric was heated 4 minutes at C. then washed withwater. The so treated fabric contained 15.7% resin and the resinremained on the fabric throughout repeated severe launderings. Thetreated fabric did not burn when held over an open flame and when theflame was removed it did not glow. The fabric retained 75% of itsoriginal warp tear strength and 100% of its original warp tensilestrength. A con siderable amount of wrinkle resistance was exhibited bythe fabric.

and two nips with a solution made from 16.4 parts of THPC, 9.9 parts ofa trimethylolmelamine, 10.3 parts of Rayon worsted fabric was treatedexactly as described for cotton twill in Example 5 except that thesolution was made from 20 parts of THPC, 12.1 parts of atrimethylolrnelamine, 12.5 parts of urea and 3.5 parts oftriethanolamine. The treated rayon contained about 20% resin and had avery high degree of wrinkle resistance, it was flameproof (passedFederal specification #CCC-T-19lb. No. 5702). It retained essentiallyall of its original tensile and tear strength.

Example 17 Wool worsted fabric wetted with a solution containing 16parts THPC, 10 parts of a trimethylolmelamine, 12 parts of urea, onepart of diethanolamine and 51 parts of water, then passed throughsqueeze rolls, dried at 95 C. and cured 4 minutes at 140 C. The fabriccontained 20% resin and was flameproof. The fabric hand was about thesame as before it was treated.

Example 18 Ramie fabric was treated in exactly the same solution andusing the same procedure as described in the above example. The ramiefabric contained 25% resin and was flameproof.

Example 19 Filter paper was padded through a solution containing thesame reagents and the same amounts of reagents described in Example 15.The paper was dried at 70 C. then cured 4 minutes at 140 C. It contained14.7% resin after it had been washed and dried. It was flameresistant.

Example 20 Burlap was wetted in the solution described in Example 17then passed through squeeze rolls, dried at 100 C., then cured 4 minutesat C. After washing and drying the burlap contained 10% resin and wasflameproof.

Example 21 When 3.5 parts of cetylamine dissolved in 30 parts of 60%ethanol were added to 2 parts of THPC dissolved in 12 parts of 80%ethanol containing 0.3 part of sodium carbonate, a low melting polymercame down almost immediately. The white polymer which would melt at lessthan 100 C. was soluble in Stoddard solvent but insoluble in water andin ethanol. The polymer contained 5.6% phosphorus and 4.4% nitrogen.

Example 22 A low melting polymer was obtained by mixing aqueoussolutions containing one part of THPC in 4 parts of Water and one partof cyclohexylamine in 4 parts of water. When the polymer was heated for15 to 20 minutes at 145 C. it formed a light brown liquid which wouldsolidify or remelt at 70 to 80 C. The polymer was insoluble in water butwas readily soluble in dioxane.

We claim:

1. A process of producing polymers, which comprises, reacting phosphoruscompounds, selected from the group consisting of tetrakis(hydroxymethyl)phosphonium chloride, tris(hydroxymethyl) phosphine oxide, and mixturesthereof, with monomeric compounds containing at least two members of thegroup consisting of hydrogen atoms and methylol (-CHzOI-I) radicalsattached to trivalent nitrogen atoms by heating at a temperature fromabout room temperature to about 150 C. in the presence of a solvent.

2. Compositions for treating hydrophilic fibrous organic materialsselected from the group consisting of cotton, jute, ramie, hemp, wool,rayon, and mixtures thereof, which compositions comprise, homogeneousaqueous mixtures consisting essentially of partially reacted mixtures ofphosphorus compounds, selected from the group consisting oftetrakis(hydroxymethyl) phosphonium chloride, tris(hydroxymethyl)phosphine oxide, and mixtures thereof, with monomeric compoundscontaining at least two members of the group consisting of hydrogenatoms and methylol (CH2OH) radicals attached to trivalent nitrogenatoms.

3. Processes of treating hydrophilic fibrous organic materials selectedfrom the group consisting of cotton, jute, ramie, hemp, wool, rayon, andmixtures thereof,

1 which processes comprise, impregnating said fibrous organic materialswith homogeneous aqueous mixtures consisting essentially of partiallyreacted mixtures of phosphorus compounds, selected from the groupconsisting of tetrakis(hydroxymethyl) phosphonium chloride,tris(hydroxymethyl) phosphine oxide, and mixtures thereof, withmonomeric compounds containing at least two members of the groupconsisting of hydrogen atoms and methylol (-CH2OH) radicals attached totrivalent nitrogen atoms and thermally inducing the completion of thereaction of said partially reacted mixtures with which said fibrousorganic materials are impregnated.

4. A process of producing cross linked polymers comprising reactingphosphorus compounds, selected from the group consisting oftetrakis(hydroxymethyl) phosphonium chloride, tris(hydroxymethyl)phosphine oxide, and mixtures thereof, in the presence of a solvent andan amount of a basic compound equivalent to the amount of chlorinepresent in the amount of tetrakis(hydroxymethyl) phosphonium chlorineused, with monomeric compounds containing at least two members of thegroup consisting of hydrogen atoms and methylol (CH2OH) radicalsattached to trivalent nitrogen atoms by heating at a temperature fromabout room temperature to about 150 C.

5. A process of producing cross linked polymers comprising reactingtris(hydroxymethyl) phosphine oxide with monomeric compounds containingat least two members of the group consisting of hydrogen atoms andmethylol (--CH2OH) radicals attached to trivalent nitrogen atoms byheating at a temperature from about room temperature to about 150 C. inthe presence of a solvent.

6. A process of producing cross linked polymers comprising reactingphosphorous compounds of the group consisting of tetrakis(hydroxymethyl)phosphonium chloride, tris(hydroxymethyl) phosphine oxide, and mixturesthereof with primary alkylamines by heating at a temperature from aboutroom temperature to about 150 C. in the presence of a solvent.

7. A process of producing cross-linked polymers comprising heatingtetrakis(hydroxymethyl) phosphonium chloride with monomeric compoundscontaining at least two members of the group consisting of hydrogenatoms and methylol (CH2OH) radicals attached to trivalent nitrogen atomsat a temperature from about room temperature to about 150 C. in thepresence of a solvent.

8. A process of reducing the flammability of textiles selected from thegroup consisting of cotton, jute, ramie, hemp, wool, rayon, and mixturesthereof which comprises impregnating the textile with an aqueoussolution of tetrakis(hydroxymethyl) phosphonium chloride,trimethylolmelamine, urea and triethanolamine, drying the material andheating the dried impregnated material for from about 130 to 160 C. forfrom about 1 to 5 minutes, using the longer times with the lowertemperatures.

9. A condensation polymer obtained by heating a mixture oftris(hydroxymethyl) phosphine oxide and 10 tetrakis(hydroxymethyl)phosphonium chloride with nitrogen compounds selected from the groupconsisting of melamine, urea, water-soluble methylol melamine, andwater-soluble methylolureas, in the presence of a solvent, at atemperature of from about room temperature to about C.

10. A process of producing cross-linked polymers containing pentavalentphosphorus radicals comprising heating in the presence of a solvent, amixture of tetrakis- (hydroxymethyl) phosphonium chloride,tris(hydroxymethyl) phosphine oxide, and monomeric compounds containingat least two members of the group consisting of hydrogen atoms andmethylol (CH2OH) radicals attached to trivalent nitrogen atoms at atemperature of from about room temperature to 150 C.

11. A condensation polymer of tris(hydroxymethyl) phosphine oxide andmelamine obtained by heating tris- (hydroxymethyl) phosphine oxide andmelamine together at a temperature from about room temperature to about150 C. in the presence of a solvent.

12. A condensation polymer of tris(hydroxymethyl) phosphine oxide andcetylamine obtained by heating tris- (hydroxymethyl) phosphine oxide andcetylamine together at a temperature from about room temperature to 150C. in the presence of a solvent.

13. A condensation polymer of tetrakis(hydroxymethyl) phosphoniumchloride, a water soluble methylolmelamine, urea, and diethanolamineobtained by heating tetrakis(hydroxymethyl) phosphonium chloride, awatersoluble methylolmelamine, urea, and diethanolamine at a temperaturefrom about room temperature to about 150 C. in the presence of asolvent.

14. A process for producing cross-linked polymers comprising heating, inthe presence of a solvent, a phosphorus compound selected from the groupconsisting of tetrakis(hydroxymethyl) phosphonium chloride, tris-(hydroxymethyl) phosphine oxide, and mixtures thereof with at least twodifferent monomeric compounds containing at least two members of thegroup consisting of hydrogen atoms and methylol (CH2OH) radicalsattached to trivalent nitrogen atoms at a temperature from about roomtemperature to about 150 C.

15. A condensation polymer of tetrakis(hydroxymethyl) phosphoniumchloride with a compound selected from the group consisting of melamine,urea, water soluble methylolmelamines, and water soluble methylolureasobtained by heating tetrakis(hydroxymethyl) phosphonium and a compoundselected from the group consisting of melamine, urea, water solublemethylolmelamines, and water soluble methylureas to a temperature fromabout room temperature to about 150 C. in the presence of a solvent.

16. A condensation polymer of a phosphorus com pound selected from thegroup consisting of tetrakis(hy droxymethyl) phosphonium chloride,tris(hydroxymeth yl) phosphine oxide, and mixtures thereof withcyclohexylamine obtained by heating the said phosphorus compound withcyclohexylamine, in the presence of a solvent, at a temperature fromabout room temperature to about 150 C.

17. A condensation polymer of a phosphorus con:- pound selected from thegroup consisting of tetrakis(hydroxymethyl) phosphonium chloride,tris(hydroxymethly) phosphine oxide, and mixtures thereof and analicyclic amine obtained by heating said phosphorus compound with thealicyclic amine, in the presence of a solvent, at a temperature fromabout room temperature to about 150 C.

18. A condensation polymer of a phosphorus cornpound selected from thegroup consisting of tetrakis(hydroxymethyl) phosphonium chloride,tris(hydroxymethyl) phosphine oxide, and mixtures thereof and anaromatic amine obtained by heating said phosphorus compound with thearomatic amine, in the presence of a solvent, at a temperature fromabout room temperature to about 150 C.

11 19. A condensation polymer of a phosphorus compound selected from thegroup consisting of tetrakis(hy droxymethyl) phosphonium chloride,tris(hydroxyrnethyl) phosphine oxide, and mixtures thereof with a cyclicirnine obtained by heating said phosphorus compound with the cyclicimine, in the presence of a solvent, at a temperature from about roonitemperature to about 150 C.

References Cited in the file of this patent UNITED STATES PATENTS

1. A PROCESS OF PRODUCING POLYMERS, WHICH COMPRISES, REACTING PHOSPHORUSCOMPOUNDS, SELECTED FROM THE GROUP CONSISTING OF TETRAKIS(HYDROXYMETHYL)PHOSPHONIUM CHLORIDE, TRIS(HYDROXYMETHYL) PHOSPHINE OXIDE, AND MIXTURESTHEREOF, WITH MONOMERIC COMPOUNDS CONTAINING AT LEAST TWO MEMBERS OF THEGROUP CONSISTING OF HYDROGEN ATOMS AND METHYLOL (-CH2OH) RADICALSATTACHED TO TRIVALENT NITROGEN ATOMS BY HEATING AT A TEMPERATURE FROMABOUT ROOM TEMPERATURE TO ABOUT 150*C. IN THE PRESENCE OF A SOLVENT.